CN114933575B - Method for preparing alpha-acetyl-gamma-butyrolactone - Google Patents
Method for preparing alpha-acetyl-gamma-butyrolactone Download PDFInfo
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- CN114933575B CN114933575B CN202210277861.9A CN202210277861A CN114933575B CN 114933575 B CN114933575 B CN 114933575B CN 202210277861 A CN202210277861 A CN 202210277861A CN 114933575 B CN114933575 B CN 114933575B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/584—Recycling of catalysts
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Abstract
A method for preparing alpha-acetyl-gamma-butyrolactone relates to the technical field of organic synthesis, gamma-butyrolactone and acetic anhydride are used as raw materials, a co-catalytic system formed by DMAP and tripropylamine is used for catalytic reaction, and the reaction is carried out at the temperature of 95-110 ℃ for 3-6 hours to obtain the product alpha-acetyl-gamma-butyrolactone. The invention has the beneficial effects that: compared with the prior art, the method has the advantages of mild reaction conditions, no use of a high-pressure container, simple treatment of reaction products, no use of dangerous raw materials such as ethylene oxide, sodium methoxide and the like, greenness, safety and environmental protection, and suitability for industrial production.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for preparing alpha-acetyl-gamma-butyrolactone.
Background
The alpha-acetyl-gamma-butyrolactone is an important intermediate for synthesizing medicines and pesticides, has large-scale industrial production abroad, is developed only in the country for about 30 years, and is mainly produced by manufacturers such as Zhejiang, jiangsu, shanxi and Hubei provinces. And the total domestic production value is not high, and most of the products are self-produced and self-used and are not out of stock. Therefore, the research on the synthesis of the compound has great significance.
The current preparation route of alpha-acetyl-gamma-butyrolactone mainly comprises the following two steps: US 5789603 reports a Claisen condensation process of gamma-butyrolactone with acetate as raw material, sodium alkoxide as condensing agent and corresponding acetate or benzene compound as solvent, which requires to be carried out in a high-pressure reactor, and has higher requirements on reaction equipment, lower safety factor of operation and low yield. Chinese patent CN101092407B proposes a method for preparing α -acetyl- γ -butyrolactone by continuously injecting vaporized γ -butyrolactone and ethyl acetate into a reactor equipped with a supported alkali fluoride catalyst and a fixed bed, the reaction is a gas phase reaction, the energy consumption is high, and the solid alkali fluoride catalyst has a certain hidden trouble for environmental pollution.
U.S. patent 2443827 reports a closed loop process wherein ethyl acetoacetate is condensed with ethylene oxide, the process requires that the reaction temperature must be below 0 ℃, that ethyl acetoacetate is readily saponified to form sodium acetoacetate at higher temperatures, that the reaction yield is affected, and that flammable and explosive ethylene oxide is used as the starting material. In the existing patents or documents, as reported in Chinese patent CN 103360349A, gamma-butyrolactone and ethyl acetate are adopted as raw materials to react with calcium oxide; the Chinese patent CN 108658902A reports that gamma-butyrolactone and ethyl acetate are adopted as raw materials to react with liquid acetaldehyde; the Chinese patent CN 108299345A reports that gamma-butyrolactone and isopropyl acetate are adopted as raw materials to react with liquid acetaldehyde; the method has the common problems of more reaction steps, harsh reaction conditions, long reaction time, difficult product separation, great environmental pollution and the like. Therefore, it is imperative to find a safe, green and convenient production process.
Disclosure of Invention
In order to overcome the defects existing in the prior art, the invention provides a method for preparing alpha-acetyl-gamma-butyrolactone. The method has the advantages of mild reaction, no use of a high-pressure container, short reaction time, low separation difficulty, high yield and good industrial application prospect.
The invention provides a method for preparing alpha-acetyl-gamma-butyrolactone, which takes gamma-butyrolactone and acetic anhydride as raw materials, takes DMAP and tripropylamine to form a co-catalytic system for catalytic reaction, and carries out heat preservation reaction for 3-6h at 95-110 ℃ to obtain the product alpha-acetyl-gamma-butyrolactone.
The preparation method comprises the steps of adding gamma-butyrolactone, tripropylamine and DMAP into a reaction container, heating to 45-50 ℃, dropwise adding acetic anhydride into the reaction container, keeping the temperature between 45 and 55 ℃ in the dropwise adding process, heating to 95-110 ℃ after the dropwise adding is finished, carrying out heat preservation reaction for 3-6 hours at 95-110 ℃, cooling to room temperature after the reaction is finished, filtering, washing a filter cake with gamma-butyrolactone, merging and carrying out reduced pressure rectification to obtain gamma-butyrolactone and alpha-acetyl-gamma-butyrolactone respectively, wherein the gamma-butyrolactone can be recycled.
In the preparation method, the excessive gamma-butyrolactone is added, and the excessive gamma-butyrolactone is used as a reaction solvent, namely the gamma-butyrolactone is used as a reactant and a reaction solvent.
Preferably, the molar ratio of the gamma-butyrolactone to the acetic anhydride is as follows: 3-5:1-2.
Preferably, the molar ratio of the acetic anhydride to tripropylamine to DMAP is as follows: 1:1:0.01-0.06.
Preferably, the molar ratio of the acetic anhydride to tripropylamine to DMAP is as follows: 1:1:0.03-0.05.
Preferably, the heat preservation reaction time is 4-5h, and the temperature is 100-105 ℃.
The invention has the beneficial effects that: (1) DMAP is used as a catalyst and forms a co-catalytic system with tripropylamine, so that the reaction is mild, and dangerous containers such as an autoclave and the like are avoided. (2) The reaction product is easy to process, does not use an organic solvent for extraction, does not need secondary distillation, saves cost and also avoids environmental pollution. (3) The gamma-butyrolactone is adopted as the solvent, so that the cost is saved, and the environmental pollution caused by introducing the solvent is avoided.
Compared with the prior art, the method has the advantages of mild reaction conditions, no use of a high-pressure container, simple treatment of reaction products, no use of dangerous raw materials such as ethylene oxide, sodium methoxide and the like, greenness, safety and environmental protection, and suitability for industrial production.
Description of the embodiments
Example 1 to a three-necked flask, 258.27g (3.0 mol) of gamma-butyrolactone, 143.27g (1.0 mol) of tripropylamine, and 6.1g (0.05 mol) of DMAP were added, the temperature was raised to 45℃to 50℃and 102.1g (1 mol) of acetic anhydride was started to be added dropwise to the flask, the temperature was kept at 45℃to 55℃during the dropwise addition, the temperature was raised to 105℃after the completion of the dropwise addition, the reaction was allowed to stand for 4.5 hours at the end of the thermal insulation, the reaction was allowed to stand still at room temperature, the mixture was filtered, the cake was washed with gamma-butyrolactone, and the mixture was distilled under reduced pressure to give a product having a boiling point of 253℃and the gamma-butyrolactone obtained during the distillation was recovered for reuse. 104.57g of the obtained product has a gas phase purity of 99.3% and a reaction yield of 40.85%.
Example 2 to a three-necked flask, 430.45g (5.0 mol) of gamma-butyrolactone, 286.54g (2.0 mol) of tripropylamine, and 14.64g (0.12 mol) of DMAP were added, the temperature was raised to 45℃to 50℃to start dropping 204.18g (2.0 mol) of acetic anhydride into the three-necked flask, the temperature was kept at 45℃to 55℃during the dropping, after the dropping was completed, the temperature was raised to 110℃to keep the temperature for 4 hours, after the reaction was completed, the reaction was cooled to room temperature, filtered, the cake was washed with gamma-butyrolactone, and the product having a boiling point of 253℃was obtained by pressure-reducing rectification, and the gamma-butyrolactone obtained during the rectification was recovered for reuse. 195.76g of the obtained product has a gas phase purity of 99.1% and a reaction yield of 38.23%.
258.27g (3.0 mol) of gamma-butyrolactone, 143.27g (1.0 mol) of tripropylamine and 3.66g (0.03 mol) of DMAP are added into a three-port bottle, the temperature is raised to 45-50 ℃, 112.3g (1.1 mol) of acetic anhydride is dropwise added into the three-port bottle, the temperature is kept between 45-55 ℃ in the dropwise adding process, the temperature is raised to 95 ℃ after the dropwise adding process is finished, the reaction is kept for 6 hours, the reaction is finished, the reaction is cooled to room temperature and filtered, a gamma-butyrolactone filter cake is washed by gamma-butyrolactone, the products with the boiling point of 253 ℃ are obtained after the filtration and the rectification are combined, and the gamma-butyrolactone obtained in the rectification process can be recycled. 110.52g of the obtained product had a gas phase purity of 99.5% and a reaction yield of 39.25%.
Claims (7)
1. A method for preparing alpha-acetyl-gamma-butyrolactone is characterized in that gamma-butyrolactone and acetic anhydride are used as raw materials, a co-catalytic system formed by DMAP and tripropylamine is used for catalytic reaction, and the reaction is carried out at the temperature of 95-110 ℃ for 3-6 hours to obtain the product alpha-acetyl-gamma-butyrolactone.
2. The method for preparing the alpha-acetyl-gamma-butyrolactone according to claim 1, wherein the preparation method of the alpha-acetyl-gamma-butyrolactone is characterized in that gamma-butyrolactone, tripropylamine and DMAP are added into a reaction container, acetic anhydride is dropwise added into the reaction container after the temperature is raised to 45-50 ℃, the temperature is kept between 45 and 55 ℃ in the dropwise adding process, the temperature is raised to 95-110 ℃ after the dropwise adding process is finished, the reaction is carried out for 3-6 hours at the temperature of 95-110 ℃, the reaction is cooled to room temperature after the reaction is finished, the filtration is carried out, a filter cake is washed by gamma-butyrolactone, and the gamma-butyrolactone and the alpha-acetyl-gamma-butyrolactone are respectively obtained after the merging and the reduced pressure rectification.
3. A process for preparing α -acetyl- γ -butyrolactone according to claim 2, wherein the γ -butyrolactone is added in excess, the excess being the reaction solvent, i.e. γ -butyrolactone is both the reactant and the reaction solvent.
4. A process for preparing α -acetyl- γ -butyrolactone according to claim 3, wherein the molar ratio of γ -butyrolactone to acetic anhydride is: 3-5:1-2.
5. The method for preparing alpha-acetyl-gamma-butyrolactone according to claim 4, wherein the molar ratio of acetic anhydride to tripropylamine to DMAP is: 1:1:0.01-0.06.
6. The method for preparing alpha-acetyl-gamma-butyrolactone according to claim 5, wherein the molar ratio of acetic anhydride to tripropylamine to DMAP is: 1:1:0.03-0.05.
7. The method for preparing α -acetyl- γ -butyrolactone according to claim 6, wherein the incubation time is 4-5h and the temperature is 100-105 ℃.
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| CN202210277861.9A CN114933575B (en) | 2022-03-21 | 2022-03-21 | Method for preparing alpha-acetyl-gamma-butyrolactone |
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| CN114933575B true CN114933575B (en) | 2023-06-16 |
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| DE19606975A1 (en) * | 1996-02-24 | 1997-08-28 | Huels Chemische Werke Ag | Process for the preparation of 2-acetyl-gamma-butyrolactone |
| CN108129423A (en) * | 2018-02-09 | 2018-06-08 | 东北制药集团股份有限公司 | A kind of method for preparing α-acetyl-gamma-butyrolacton |
| CN114195745A (en) * | 2021-12-29 | 2022-03-18 | 江苏兄弟维生素有限公司 | Preparation method and application of alpha-acetyl-gamma-butyrolactone |
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